Mixtures of Fibre-Reactive Dyes and Their Use in a Method for Trichromatic Dyeing or Printing

ABSTRACT

Dye mixtures, comprising least one yellow dye of the formula (1), at least one yellow dye of the formula (2), at least one red dye of the formula (3), at least one blue dye of the formula (4), wherein the radicals have the definitions given in the claims, are suitable especially for the trichromatic dyeing or printing of cellulosic fibre materials and yield dyeings or prints having good reproducibility and good all-round fastness properties.

The present invention relates to mixtures of reactive dyes that are suitable for the dyeing or printing of nitrogen-containing or hydroxy-group-containing fibre materials and yield on such materials dyeings or prints having good reproducibility and good all-round fastness properties. The present invention relates also to a method for trichromatic dyeing or printing wherein the reactive dye mixtures according to the invention are used.

There is a huge demand for novel reactive dye mixtures that are suitable for the reproducible trichromatic dyeing and printing of fibre materials which fulfill highest ecological and economical requirements while still providing dyeings of the desired colour shades with good fastness properties, such as wash and water fastness and perspiration fastness. Suitable reactive dyes should provide a unique combinability and a low sensitivity to various dyeing parameters. Furthermore, they should have sufficient substantivity and at the same time have good ease of washing off of unfixed dye. They should also have a good tinctorial yield and high reactivity, the objective being to provide especially dyeings having high degrees of fixation.

The present invention is therefore based on the problem of providing new mixtures of reactive dyes that are suitable especially for the reproducible trichromatic dyeing and printing of fibre materials in the desired colour shades and fulfill the above indicated requirements to the highest possible extent.

The present invention accordingly relates to a dye mixture, comprising at least one yellow dye of the formula

wherein Ar₁ represents a benzene or naphthalene radical, X₁ is chlorine or fluorine, R₁ is amino or C₁-C₆alkyl, R₂, R₃, R₄, R₅, R₆ and R₇ each independently of the others represent hydrogen, hydroxy, amino, C₁-C₆alkyl, C₁-C₆alkoxy or sulfo, u is a number from 1 to 3, Y is vinyl or a radical —CH₂—CH₂—U and U is a group removable under alkaline conditions; at least one yellow dye of the formula

wherein Ar₂ represents a benzene or naphthalene radical, X₂, and X₃ independently of the other are chlorine or fluorine, B denotes a straight-chain or branched C₂-C₆alkylene radical which is unsubstituted or substituted by hydroxy, sulfo or sulfato, R₈, R₉, R₁₀ and R₁₁ each independently of the others represent hydrogen or C₁-C₆alkyl which is unsubstituted or substituted by hydroxy, amino, cyano, halogen, C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl, carboxyl, sulfamoyl, sulfo or sulfato, R₁₂ and R₁₃, denote amino or C₁-C₆alkyl, R₁₄, R₁₅ and R₁₆ each independently of the others are hydrogen, hydroxy, amino, C₁-C₆alkyl, C₁-C₆alkoxy or sulfo, v is a number from 1 to 3; at least one red dye of the formula

wherein Ar₃ represents a benzene or naphthalene radical, X₄ denotes halogen, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl, R₁₇ is hydrogen or C₁-C₆alkyl, R₁₈ represents hydrogen, C₁-C₆alkyl, C₁-C₆alkoxy or sulfo, Z₁ is hydrogen or a fibre-reactive group of the formula

—SO₂—Y₂,  (7a)

or —NH—CO—(CH₂)₂₋₃—SO₂—Y₃  (7b),

Y₁, Y₂ and Y₃ each independently of the others denote vinyl or a radical —CH₂—CH₂—U and U is a group removable under alkaline conditions, and k is a number from 1 to 3; and at least one blue dye of the formula

wherein (R₁₉)_(b) denotes b identical or different substituents from the group C₁-C₆alkyl, C₁-C₆alkoxy, sulfo and halogen, X₅ is halogen, Z₂ is a fibre-reactive radical of formula

—SO₂—Y₄  (5a),

—NH—CO—(CH₂)_(m)—SO₂—Y₅  (5b),

—CONN—(CH₂)_(n)—SO₂—Y₆  (5c),

—NH—CO—CH(Hal)-CH₂-Hal  (5d),

—NH—CO—C(Hal)=CH₂  (5e) or

wherein H₂ is halogen, a non-fibre-reactive substituent or a fibre-reactive radical of formula

NH—(CH₂)₂₋₃—SO₂—Y₇  (6a),

—NH—(CH₂₋₃—O—(CH₂)₂₋₃—SO₂—Y₈  (6b),

(R₂₀)₀₋₂ denotes from 0 to 2 identical or different substituents from the group halogen, C₁-C₆-alkyl, C₁-C₆alkoxy and sulfo, Y₄, Y₅, Y₆, Y₇, Y₈, Y₉ and Y₁₀ each independently of the others denote vinyl or a —CH₂—CH₂—U radical and U is a group that is removable under alkaline conditions, Q is a —CH(Hal)-CH₂-Hal or —C(Hal)=CH₂ group, m and n are each independently of the other the number 2, 3 or 4 and Hal is halogen, T₁ is a fibre-reactive radical of the above formula (6b), (6c), (6d) or (6e) and b and a are each independently of the other the number 0, 1 or 2.

The dyes of the formulae (1), (2), (3) and (4) in the dye mixtures according to the invention contain one or more than one sulfo group or carboxy group, which are each present either in free acid form or, preferably, in salt form. Suitable salts are, for example, alkali metal, alkaline earth metal or ammonium salts, salts of an organic amine, or mixtures thereof. Examples that may be mentioned are ammonium, lithium or, preferably sodium or potassium salts, or in the form of a salt of an organic amine, for example, a mono-, di- or tri-ethanolamine salt or mixed Na/Li or Na/Li/NH₄ salts.

C₁-C₆alkyl groups which come into consideration for R₁ to R₂₀ can be e.g. methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl and n-hexyl, preferably methyl and ethyl.

Suitable C₁-C₆alkoxy groups as R₂ to R₁₁ and R₁₄ to R₂₀ are e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy and n-hexoxy, preferably, methoxy and ethoxy and, especially, methoxy.

As leaving group U there comes into consideration, for example, —Cl, —Br, —F, —OSO₃H, —SSO₃H, —OCO—CH₃, —OPO₃H₂, —OCO—C₆H₅, —OSO₂—C₁-C₄alkyl or —OSO₂—N(C₁-C₄alkyl)₂. U is preferably a group of the formula —Cl, —OSO₃H, —SSO₃H, —OCO—CH₃, —OCO—C₆H₅ or —OPO₃H₂, especially —Cl or —OSO₃H.

Examples of preferred bridging moieties B in formula (2) are ethylene, propylene, trimethylene, 2-hydroxypropanediyl, tetramethylene, 2,2-dimethylpropanediyl, 2-methylpentanediyl and hexamethylene.

Halogen as substituent X₄, X₅ or T₂ can be fluorine, chlorine or bromine, in particular fluorine or chlorine.

Halogen as Hal in formula (5d), (5e) or (6e) may be chlorine or bromine, in particular bromine.

Ar₁ in formula (1) is preferably naphthyl substituted by three sulfo groups.

R₁ in formula (1) is preferably amino or methyl, especially amino.

R₂ in formula (1) is preferably hydrogen.

R₃ in formula (1) is preferably hydrogen.

R₄ in formula (1) is preferably amino.

R₅ in formula (1) is preferably sulfo.

R₆ and R₇ in formula (1) are preferably hydrogen.

In formula (2) R₈, R₉, R₁₀ and R₁₁ preferably represent hydrogen.

R₁₂ and R₁₃ are preferably amino.

Ar₂ in formula (2) is preferably naphthyl substituted by three sulfo groups.

Preferably B in formula (2) preferably represents ethylene, propylene or trimethylene, in particular trimethylene.

Ar₃ in formula (3) is preferably naphthyl substituted by two sulfo groups.

Preferably Z₁ is hydrogen.

Y₁ is preferably vinyl or 2-sulfatoethyl.

R₁₇ in formula (3) is preferably hydrogen or ethyl, in particular hydrogen.

R₁₈ in formula (3) is preferably hydrogen.

In formula (4) Z₂ preferably represents vinylsulfonyl, 2-sulfatoethylsulfonyl or —NHCO—CBr═CH₂Br.

R₁₉ is preferably sulfo and b is 0 or 1.

a in formula (4) is preferably 1.

T₁ in formula (4) is preferably a radical of formula (6c) wherein Y₉ is vinyl or 2-sutfatoethyl.

Preference is given to dye mixtures, wherein the dye of the formula (1) corresponds to the compound of the formula

Suitable dyes of formula (2) are, for example, the compounds of the formulae

Preference is given to dye mixtures, wherein the dye of the formula (2) corresponds to the compound of the formula (201).

In addition to the dyestuffs of formulae (1) and (2), the mixtures according to the invention may contain further yellow reactive dyes, like e.g. the dye of the formulae

Suitable dyes of formula (3) are, for example, the compounds of the formulae

Preference is also given to dye mixtures, wherein the dye of the formula (3) corresponds to the compound of the formula (301).

Preference is also given to dye mixtures, wherein the dye of the formula (3) corresponds to the compound of the formula (302).

In a preferred embodiment the trichromatic mixtures according to the invention contains as red component a mixture of a dye of formula (301) and a dye of formula (302).

Suitable dyes of formula (4) are, for example, the compounds of the formulae

In addition to the blue dyestuffs of formulae (4), the mixtures according to the invention may contain further blue reactive dyes, like e.g. the dyes of the formula

wherein Z₃ is a fibre-reactive radical of formula (5a), (5b), (5c), (5d), (5e) or (5f) as defined above.

The dye of formula (8) is, for example, a dye of the formula

The dye of formula (801) is particularly preferred.

In a preferred embodiment the mixture according to the invention contains the dye of formula (101) and the dye of formula (201) as defined above in a weight ratio from 4:1 to 1:4, preferably from 2:1 to 1:2, and in particular in a weight ratio from 1:1 to 1:2.

In a further preferred embodiment the mixture according to the invention contains the dye of formula (302) and the dye of formula (301) as defined above in a weight ratio from 4:1 to 1:4, preferably from 2:1 to 1:2, and in particular in a weight ratio from 2:1 to 1:1.

In a further preferred embodiment the mixture according to the invention contains the dye of formula (401) and the dye of formula (801) as defined above in a weight ratio from 4:1 to 1:4, preferably from 2:1 to 1:2, and in particular in a weight ratio from 1:1 to 1:2.

A particularly preferred embodiment of the invention is a trichromatic dye mixture comprising as yellow component a mixture of a dye of formula (101) and a dye of formula (201) as defined above, as red component a mixture of a dye of formula (301) and a dye of formula (302) as defined above and as blue component a mixture of a dye of formula (401) and a dye of formula (801) as defined above.

The dyes of formulae (1), (2), (3), (4) and (8) are known in some cases or they can be prepared in accordance with processes known per se. Dyes of the formula (1) are disclosed, for example, in EP 623 655. Dyes of the formula (2) are disclosed, for example, in EP 478 503. Dyes of the formulae (3) and (4) are disclosed, for example, in U.S. Pat. No. 7,641,724. Dyes of the formula (8) are disclosed, for example, in WO 2005/090485.

The dye mixtures according to the invention can be prepared, for example, by mixing the individual dyes together. The mixing procedure is effected, for example, in suitable mills, e.g. ball mills or pin mills, as well as in kneaders or mixers. The dye mixtures according to the invention can also be prepared, for example, by dissolving the reactive dyes directly in the dyebath or the printing medium. The amount of the individual reactive dyes is governed by the shade to be obtained. The dye of formula (1) and the total amount of the dyes of formulae (2), (3), (4) and (8) are present in the dye mixtures according to the invention in a ratio by weight of, for example, from 1:99 to 99:1, preferably from 5:95 to 95:5 and especially from 10:90 to 90:10.

The reactive dyes of formulae (1), (2), (3), (4) and (8) and accordingly also the dye mixtures according to the invention may comprise further additives, for example, sodium chloride or dextrin.

If desired, the reactive dyes of formulae (1), (2), (3), (4) and (8) and accordingly also the dye mixtures according to the invention may comprise further auxiliaries which, for example, improve handling or increase storage stability, such as buffers, dispersants or anti-dusts. Such auxiliaries are known to the person skilled in the art.

The dye mixtures according to the invention are suitable for the dyeing and printing of an extremely wide variety of materials, especially hydroxy-group-containing or nitrogen-containing fibre materials. Examples thereof are paper, silk, leather, wool, polyamide fibres and polyurethanes as well as, especially, cellulosic fibre materials of all kinds. Such fibre materials are, for example, natural cellulose fibres, such as cotton, linen and hemp, as well as cellulose and regenerated cellulose. The dye mixtures according to the invention and the reactive dyes according to the invention are also suitable for the dyeing or printing of hydroxy-group-containing fibres that are contained in blend fabrics, for example mixtures of cotton with polyester fibres or polyamide fibres.

The said textile fibre material may be in an extremely wide variety of processing forms, such as, for example, in the form of fibres, yarn, woven fabric or knitted fabric.

The present invention relates also to a method for the trichromatic dyeing or printing of hydroxy-group-containing or nitrogen-containing fibre materials, especially cellulosic fibre materials, which method comprises using at least one yellow dye, for example one, two or three dyes, preferably one dye, of the above-mentioned formula (1) and at least one yellow dye, for example one, two or three dyes, preferably one dye, of the above-mentioned formula (2), together with at least one red dye of the above-mentioned formula (3) and at least one blue dye of the above-mentioned formula (4).

The method according to the invention for trichromatic dyeing and printing can be carried out in accordance with customary dyeing and printing methods, for example, according to the so-called cold pad-batch process, in which the dye is applied, together with the alkali, on the padder and is then fixed by storage for several hours at about room temperature, for example, from 25 to 35° C. Preferably, the method according to the invention for trichromatic dyeing and printing is carried out according to the exhaust-dyeing method, in which the goods are impregnated with aqueous, optionally salt-containing dye solutions, and the dyes are fixed after an alkali treatment or in the presence of alkali, optionally under the action of heat.

The dye liquors or print pastes, in addition to containing water and the dyes, may also comprise further additives, for example shading dyes known per se, salts, buffer substances, wetting agents, anti-foams, levelling agents or agents that influence the properties of the textile material, for example, softeners, additives for flame-resistant finishes or dirt-, water- or oil-repellants, as well as water-softeners and natural or synthetic thickeners, e.g. alginates or cellulose ethers.

The amounts in which the individual dyes are used in the dyebaths or print pastes can vary within wide limits in dependence upon the desired depth of shade; in general, amounts of from 0.01 to 15% by weight, especially from 0.1 to 10% by weight, based on the goods being dyed or on the print paste, have proved advantageous.

The dyes of formulae (1), (2), (3), (4) and (8) used in the method according to the invention are distinguished in trichromatic dyeing or printing by uniform colour build-up, good exhaustion and fixing behaviour, good constancy of shade even in different concentrations, a low sensitivity to various dyeing parameters and, in particular, very good combinability. Dyeing times can be reduced. Furthermore, they have sufficient substantivity and at the same time have good ease of washing off of unfixed dye and can advantageously be applied at short liquor ratios, for example, at a liquor ratio of from 1:4 to 1:6, preferably, 1:6. The dyeings and prints produced in accordance with the method of the invention exhibit very good fastness properties, such as wash and water fastness and perspiration fastness, and good reproducibility.

The following Examples serve to illustrate the invention. Unless otherwise indicated, temperatures are given in degrees Celsius, parts are parts by weight and percentages relate to percent by weight. Parts by weight relate to parts by volume in a ratio of kilograms to litres.

EXAMPLE 1

A bleached cotton tricot fabric is introduced at 60° C. into an aqueous dyebath with a liquor ratio of 1:10 which contains 72 g/l of sodium chloride, 0.541% by weight of the yellow dyeing reactive dye of formula (201), 0.361% by weight of the yellow dyeing reactive dye of formula (101), 0.276% by weight of the red dyeing reactive dye of formula (301), 0.413% by weight of the red dyeing reactive dye of formula (302), 0.618% by weight of the blue dyeing reactive dye of formula (801) and 0.412% by weight of the blue dyeing reactive dye of formula (401). A total of 15.2 g/l of calcined sodium carbonate is added in 4 portions (1.52 g/l, 3.04 g/l, 3.04 g/l and 7.6 g/l, respectively) to the dyebath after 45, 50, 55 and 60 minutes at 60° C. Dyeing is continued for 35 minutes. The dyed fabric is taken out of the dyeing liquor and dried. A brown shaded fabric is obtained.

The evolution of the shade during the dyeing steps (exhaustion and fixation) is monitored by measuring the h coordinates (CIELab sysystem) from the remission curves of the respective samples (spectrophotometer Datacolor SF 600). Independent from reaction parameters like dyeing time, temperature, amount of salt or alkali, the measured shade values vary within narrow limits, i.e. the dye mixture according to the invention allows a very good shade control.

COMPARATIVE EXAMPLE 2

A bleached cotton tricot (1-4002/22) fabric is introduced at 60° C. into an aqueous dyebath with a liquor ratio of 1:10 which contains 78 g/l of sodium chloride, 0.90% by weight of the yellow dyeing reactive dye of formula (201), 0.68% by weight of the red dyeing reactive dye of formula (301) and 1.29% by weight of the blue dyeing reactive dye of formula (801). A total of 15.8 g/l of calcined sodium carbonate is added in 4 portions (1.58 g/l, 3.16 g/l, 3.16 g/l and 7.9 g/l, respectively) to the dyebath after 45, 50, 55 and 60 minutes at 60° C. Dyeing is continued for 35 minutes. The dyed fabric is taken out of the dyeing liquor and dried. A brown shaded fabric is obtained.

The evolution of the shade during the dyeing steps (exhaustion and fixation) is monitored by measuring the h coordinates (CIELab sysystem) from the remission curves of the respective samples (spectrophotometer Datacolor SF 600). Depending on reaction parameters like dyeing time, temperature, amount of salt or alkali, the measured shade values vary within a considerable range. 

1. A dye mixture, comprising at least one yellow dye of the formula

wherein Ar₁ represents a benzene or naphthalene radical, X₁ is chlorine or fluorine, R₁ is amino or C₁-C₆ alkyl, R₂, R₃, R₄, R₅, R₆ and R₇ each independently of the others represent hydrogen, hydroxy, amino, C₁-C₆ alkyl, C₁-C₆ alkoxy or sulfo, u is a number from 1 to 3, Y is vinyl or a radical —CH₂—CH₂—U and U is a group removable under alkaline conditions; at least one yellow dye of the formula

wherein Ar₂ represents a benzene or naphthalene radical, X₂, and X₃ independently of the other are chlorine or fluorine, B denotes a straight-chain or branched C₂-C₆ alkylene radical which is unsubstituted or substituted by hydroxy, sulfo or sulfato, R₈, R₉, R₁₀ and R₁₁ each independently of the others represent hydrogen or C₁-C₆ alkyl which is unsubstituted or substituted by hydroxy, amino, cyano, halogen, C₁-C₆ alkoxy, C₁-C₆ alkoxycarbonyl, carboxyl, sulfamoyl, sulfo or sulfato, R₁₂ and R₁₃, denote amino or C₁-C₆ alkyl, R₁₄, R₁₅ and R₁₆ each independently of the others are hydrogen, hydroxy, amino, C₁-C₆ alkyl, C₁-C₆ alkoxy or sulfo, v is a number from 1 to 3; at least one red dye of the formula

wherein Ar₃ represents a benzene or naphthalene radical, X₄ denotes halogen, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl, R₁₇ is hydrogen or C₁-C₆ alkyl, R₁₈ represents hydrogen, C₁-C₆ alkyl, C₁-C₆ alkoxy or sulfo, Z₁ is hydrogen or a fibre-reactive group of the formula —SO₂—Y₂,  (7a) or —NH—CO—(CH₂)₂₋₃—SO₂—Y₃  (7b), Y₁, Y₂ and Y₃ each independently of the others denote vinyl or a radical —CH₂—CH₂—U and U is a group removable under alkaline conditions, and k is a number from 1 to 3; and at least one blue dye of the formula

wherein (R₁₉)_(b) denotes b identical or different substituents from the group C₁-C₆ alkyl, C₁-C₆ alkoxy, sulfo and halogen, X₅ is halogen, Z₂ is a fibre-reactive radical of formula —SO₂—Y₄  (5a), —NH—CO—(CH₂)_(m)—SO₂—Y₅  (5b), —CONH—(CH₂)_(n)—SO₂—Y₆  (5c), —NH—CO—CH(Hal)-CH₂-Hal  (5d), —NH—CO—C(Hal)=CH₂  (5e) or

wherein T₂ is halogen, a non-fibre-reactive substituent or a fibre-reactive radical of formula —NH—(CH₂)₂₋₃—SO₂—Y₇  (6a), —NH—(CH₂)₂₋₃—O—(CH₂)₂₋₃—SO₂—Y₈  (6b),

(R₂₀)₀₋₂ denotes from 0 to 2 identical or different substituents from the group halogen, C₁-C₆ alkyl, C₁-C₆ alkoxy and sulfo, Y₄, Y₅, Y₆, Y₇, Y₈, Y₉ and Y₁₀ each independently of the others denote vinyl or a —CH₂—CH₂—U radical and U is a group that is removable under alkaline conditions, Q is a —CH(Hal)-CH₂-Hal or —C(Hal)=CH₂ group, m and n are each independently of the other the number 2, 3 or 4 and Hal is halogen, T₁ is a fibre-reactive radical of the above formula (6b), (6c), (6d) or (6e) and b and a are each independently of the other the number 0, 1 or
 2. 2. A dye mixture according to claim 1, wherein the dye of the formula (1) corresponds to the compound of the formula


3. A dye mixture according to claim 1, wherein the dye of the formula (2) corresponds to the compound of formula


4. A dye mixture according to claim 1, wherein the dye of the formula (3) corresponds to the compound of the formula


5. A dye mixture according to claim 1, wherein the dye of the formula (3) corresponds to the compound of the formula


6. A dye mixture according to claim 1, wherein the dye of the formula (4) corresponds to the compound of the formula


7. A dye mixture according to claim 1 additionally containing a blue dye of the formula

wherein Z₃ is a fibre-reactive radical of formula (5a), (5b), (5c), (5d), (5e) or (5f) as defined in claim
 1. 8. A dye mixture according to claim 2 containing a dye of formula (101) as defined in claim 2 and a dye of formula

in a weight ratio from 4:1 to 1:4.
 9. A dye mixture according to claim 1 containing a dye of formula

and a dye of formula

in a weight ratio from 4:1 to 1:4.
 10. A dye mixture according to claim 1 containing a dye of formula

and a dye of formula

in a weight ratio from 4:1 to 1:4.
 11. A trichromatic dye mixture comprising as yellow component a mixture of a dye of formula

and a dye of formula,

as red component a mixture of a dye of formula

and a dye of formula

and as blue component a mixture of a dye of formula

and a dye of formula (801)


12. A method for the trichromatic dyeing or printing of hydroxy-group-containing or nitrogen-containing fibre materials, which method comprises using at least one yellow dye of the formula

wherein Ar₁ represents a benzene or naphthalene radical, X₁ is chlorine or fluorine, R₁ is amino or C₁-C₆ alkyl, R₂, R₃, R₄, R₅, R₆ and R₇ each independently of the others represent hydrogen, hydroxy, amino, C₁-C₆ alkyl, C₁-C₆ alkoxy or sulfo, u is a number from 1 to 3, Y is vinyl or a radical —CH₂—CH₂—U and U is a group removable under alkaline conditions; at least one yellow dye of the formula

wherein Ar₂ represents a benzene or naphthalene radical, X₂, and X₃ independently of the other are chlorine or fluorine, B denotes ethylene, propylene, trimethylene, tetramethylene, pentamethylene or hexamethylene, R₈, R₉, R₁₀ and R₁₁ each independently of the others represent hydrogen or C₁-C₆ alkyl which is unsubstituted or substituted by hydroxy, amino, cyano, halogen, C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl, carboxyl, sulfamoyl, sulfo or sulfato, R₁₂, R₁₃, R₁₄, R₁₅ and R₁₆ each independently of the others are hydrogen, hydroxy, amino, C₁-C₆ alkyl, C₁-C₆alkoxy or sulfo, v is a number from 1 to 3; at least one red dye of the formula

wherein Ar₃ represents a benzene or naphthalene radical, X₄ denotes halogen, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl, R₁₇ is hydrogen or C₁-C₆ alkyl, R₁₈ represents hydrogen, C₁-C₆ alkyl, C₁-C₆alkoxy or sulfo, Z₁ is hydrogen or a fibre-reactive group of the formula —SO₂—Y₂,  (7a) or —NH—CO—(CH₂)₂₋₃—SO₂—Y₃  (7b), Y₁, Y₂ and Y₃ each independently of the others denote vinyl or a radical —CH₂—CH₂—U and U is a group removable under alkaline conditions, and k is a number from 1 to 3; at least one blue dye of the formula

wherein (R₁₉)_(b) denotes b identical or different substituents from the group C₁-C₆ alkyl, C₁-C₆ alkoxy, sulfo and halogen, X₅ is halogen, Z₂ is a fibre-reactive radical of formula —SO₂—Y₄  (5a), —NH—CO—(CH₂)_(m)—SO₂—Y₅  (5b), —CONH—(CH₂)_(n)—SO₂—Y₆  (5c), —NH—CO—CH(Hal)-CH₂-Hal  (5d), —NH—CO—C(Hal)=CH₂  (5e) or

wherein T₂ is halogen, a non-fibre-reactive substituent or a fibre-reactive radical of formula —NH—(CH₂)₂₋₃—SO₂—Y₇  (6a), —NH—(CH₂)₂₋₃—O—(CH₂)₂₋₃—SO₂—Y₈  (6b),

(R₂₀)₀₋₂ denotes from 0 to 2 identical or different substituents from the group halogen, C₁-C₆ alkyl, C₁-C₆alkoxy and sulfo, Y₄, Y₅, Y₆, Y₇, Y₅, Y₉ and Y₁₀ each independently of the others denote vinyl or a —CH₂—CH₂—U radical and U is a group that is removable under alkaline conditions, Q is a —CH(Hal)-CH₂-Hal or —C(Hal)=CH₂ group, m and n are each independently of the other the number 2, 3 or 4 and Hal is halogen, T₁ is a fibre-reactive radical of the above formula (6b), (6c), (6d) or (6e) and b and a are each independently of the other the number 0, 1 or
 2. 13. A method according to claim 12, wherein cellulosic fibre material is dyed or printed.
 14. A method according to claim 13, wherein the cellulosic fibre material is cotton-containing fibre material. 